Perhydro bis-(isoprenyl) alkyl aryl sulfonates



United States Patent 3,196,174 Bfi-(KSGPRENYL) ALKYL ARYL SULFONATES Thepresent invention relates to new alkyl benzene hydrocarbons which areuseful in the production of biodegradable synthetic deter ents havinghighly superior washing properties. Further, this invention relates tothe economic preparation of these hydrocarbons from inexpensive feedstocks. More particularly, this invention relates to the preparation ofthese hydrocarbons by reacting an aryl substituted alkyl alkali metalcompound (preferably an arylallryl lithium compound) under carefullychosen reaction conditions to obtain the selective growth of two molesof isoprene on to the aralkyl metal, hydrolyzing to obtain thecorresponding allradienyl benzene and hydrogenating to remove theunsaturation and thus produce the desired allryl benzene material.

Illustrated in chemical notation the new alkyl benzene hydrocarbons ofthis invention may be represented by the following general formula.

wherein R is a perhydro bis (isoprenyl) alkyl radical containing tencarbon atoms comprising the structure CH QHCH -CH CH -?HCH CH but cm andZ is a two to four carbon atom alkylene group, the said alkylene groupcontaining a single methyl group branch. The alkali metal sulfonate ofthese materials is represented by the following formula:

so x wherein X is an alkali metal, preferably sodium, and R and Z are asabove described.

Illustrative examples of the hydrocarbon materials are:

Edd-6,174 Patented July 20, 1965 The alkali metal sulfonate salts ofthese alkyl benzene hydrocarbons have now been found to be highlysuperior to other similar type detergents known in the prior art. Thisis true not only with respect to the washing properties of thesedetergents but also with respect to their capacity to be removed inconventional sewage disposal plants. Thus, the present detergents havebeen found to be substantially entirely absent from the effluent fromsuch a sewage treating, having been removed by biodegradation,adsorption, and the like. This property is an extremely important factorin preventing the foaming which has been encountered particularly inEurope in rivers and streams into which the efiluent from sewagedisposal plants is discharged. It should be noted that it is surprisingthat both of these improvements are obtained at the same time byutilizing the present easily and cheaply prepared materials havingmolecular structures as above described.

It is now known that conventional alkyl benzene sulfonates commerciallyprepared by alkylating benzene with tetrapropylene prepared bypolymerizing propylene over a phosphoric acid on Kieselguhr catalyst areparticularly resistant to biological degradation by bacteria normallypresent in microorganism populations of activated sewage sludge (andthat they are not otherwise removed by adsorption, etc.). Further it isknown that severe foaming and frothing have occurred in many locationswhere sewage disposal plants discharge their efiluent into rivers andstreams. It has now been found that the detergent materials of the typedescribed in this invention are readily degraded biologically by themicroorganisms normally present in this sludge or are otherwise removedso that when processed in a sewage plant the ellluent from said planthas little or no tendency to foam.

It has now been surprisingly discovered that by the process of thepresent invention substantially fully biodegradable detergents areobtained and in addition these detergents possess substantially higherdetersive power than conventional sodium sulfonates of tetrapropylbenzene. Thus, for example, at equal concentrations approximately twice thenumber of dishes can be washed with the new detergents herein describedcompared to a conventional tetrapropyl benzene sulfonate and brightnessincreases of the same order of magnitude are obtained in tests comparingthe effectiveness of these detergents for soiled cotton cloth.Additionally, foaming power is ex ceptional without the use of thealkanolamides of fatty acids (foam builders) conventionally used incommercial detergents.

The present invention will be more clearly understood from aconsideration of the general reaction sequence as applied to preparingone of the improved detergents of the present invention. Thus, two molesof isoprene are added to or ethyl phenyl lithium by growth reaction andthe product material obtained after hydrolysis, is hydrogenated toobtain the desired saturated 2-phenyl-5,9-dimethyldecane as follows:

Alternatively, after the growth reaction the product (2) may behydrogenated directly both to remove the Li by displacement and tosaturate the double bonds.

The organolithium compounds having the general formula C H ZLi, where Zis a two to four carbon alkylene group having a single methyl branch maybe prepared by the following general methods:

(1) By reaction of a suitable halogenated alkyl benzene with metalliclithium, preferably in a finely divided state and in the presence of asuitable solvent. Temperatures of below 0 C. to about 100 C. may be useddepending on the nature of the halide or solvent and re action times offrom one to several hours may similarly vary.

(2) By reaction of a halogenated alkyl benzene with for example a loweralkyl lithium.

(3) By reaction of an alkyl benzene with an alkyl lithium compound.

C H Z--(H) +RLi C H ZLi+RH (4) By addition of an alkyl lithium compoundto an unsaturated alkyl benzene. (RH below is minus RH) (5) By metalexchange with a Grignard compound prepared from a siutable halogenatedalkyl benzene.

The preparation of organolithium compounds by the methods shown aboveand by other means is well known in the art and is not considered as anovel aspect of this invention.

Following the preparation of the aralkyl lithium com pound this materialis reacted with isoprene at pressures of from one to several hundredatmospheres, preferably one to ten atmospheres, e.g. 1 to 3 atmospheres,and at temperatures of below 0 C. to 100 C., preferably 0 C. to 50 C.,e.g. 25 C. for times of 0.25-25 hours, preferably 1-12 hours, e.g. 3-4hours. The amount of isoprene added is equal to 0.8 to 4 mols,preferably 1 to 3 mols, e.g. 2 mols of isoprene per mol of metal alkylaryl. Thus, the desired aralkadienyl metal having e.g. two mols ofisoprene added is obtained.

Following the growth reaction the product is hydrolyzed and the excesssulfuric acid into sulfate.

with water at temperautres of e.g. 0 to C. to obtain the desiredalkadienyl benzene. This hydrolysis may be carried out with or withoutan alcohol being present. If the alcohol is used, it may be added priorto the water hydrolysis. This makes the water hydrolysis less vigorous.Suitable alcohols are methanol, ethanol, isopropanol and the like. Inany case considerable heat is evolved in the preliminary hydrolysis oralcoholysis and so rather large cooling capaicty is needed.

The alkadienyl benzene is then hydrogenated by conventional means. Forexample, this material may be contacted with two to one hundred moles ofhydrogen per mole of unsaturated compound at temperatures of 25 C. to C.and pressures of one to two thousand p.s.i.g. and in the presence of anyof the hydrogenation catalysts well known to the art. Suitable catalystsare platinum, palladium and nickel, either as such or supported on acarrier. Of these the preferred catalyst is Raney nickel. Alternatively,as previously mentioned hydrogenation of the metal alkadienyl benzenecompounds directly to the desired alkyl benzenes with recovery of themetal hydride for reuse can be obtained using the above describedconditions. When the hydrogenation is completed, the product may berecovered by filtration from the catalyst and purified by distillation.It may be further purified prior to sulfonation by mild acid and claytreatment as disclosed in US. Patent 2,688,633.

The new alkyl benzenes may be sulfonated in known manner, e.g. bycontact with an excess of concentrated sulfuric acid, oleum, ClSO I-I,sulfur trioxide, etc. The sulfonation may be carried out at temperaturesup to 60 C., preferably for oleum 15 C. to 60 C., e.g. 40 C. The acidconcentration is preferably at least 98%. Acid of 100% concentration andpreferably oleum, containing up to e.g. 20 wt. percent S0 or higher, maybe employed. With higher acid concentration, lower reaction times arerequired, e.g. about 3 to 4 hours with 98% acid, about 2 hours with 100%acid, and preferably 0.5 to 1 hour, e.g. 0.7 hour, with oleum. Weightratios of sulfuric acid to hydrocarbon may range from 0.811 to 2.0: l, a1.4:1 ratio being suitable when using 20% oleum, for example. The largerthe ratio, the more inorganic sulfate will be present in the productfollowing neutralization. In many cases, the inorganic sulfate is adesirable constituent of the finished detergent composition.

The sulfonation product mixture may be separated by layering with theaddition of a limited amount of Water to remove part of the excess spentacid before neutralizing or may be neutralized directly. Whenneutralized, the sulfonic acids are thus converted to sulfonic acidsalts The neutralization may be carried out with any base orbasic-reacting inorganic or organic substance. Thus, to produce sodiumsulfonates, aqueous sodium hydroxide or sodium carbonates are suitablyemployed. Other alkali metal, alkaline earth metal, ammonium or aminesalts may be similarly produced from the corresponding basic compounds.The neutralization is generally carried out by contact with basicaqueous solution at temperatures of from 20 C. to 70 C., those between30 C. and 50 C., e.g. 50 C., being preferred.

The present invention will be more clearly understood from aconsideration of the following examples.

EXAMPLE I.SYNTHESIS OF Z-PHENYL 5,9-DIMETHYLDECANE 2-phenyl5,9-dimethyldecane was synthesized by the following series of steps.

OCCCGCC-OOH PBra 1-bromo-3,7-dimethy1oetane 2'phenyl5,9-dimethyldecene-2(3) 2-phenyl5,9-dhnethyldemnol-Z 2 (4) 2 phe11yl 5,9-dimethyldecene-2 W2-phenyl-5,9-dirnethyldccane (1 1-bromo-3,7-dimethy[octane One mole (158grns.) of 3,7-dimethyloctanol-1 (8.1. 114 C. 20 torr fi /D 1.4369) madeby the hydrogenation of citronellol over Raney nickel was reacted at 5to C. with 100 grams of PBIg followed by heating on a water bath at 70C. for 2 hours. The mixture was then distilled rapidly at low pressure(1 mm.) to a pot temperature of 125 C. to'obtain a distillate weighing177 gms. and a residue (P(()H) of 50 grams. T .e distillate Wasextracted twice with 50 ml. portions of ice-cold 96% H 80 neutralizedwith NHgOH and extracted with methanol. The product was dried over K COand distilled at reduced pressure. B.P. 4445 C. 0.4 torr. Yield 156grams=70%.

(2) 2-pizenyl-2-hydr0xy-5,9-dimet!zylciccane 155 grams (0.7 mole) of theabove bromide was Grig- (3) Z-pizenyZ-5,9-dimethyldecene-Z 136 gm. ofthe phenyl hydroxy decane was dehydrated by retiuxng with 500 ml. of 60wt. percent H 59 for 4 hours. After isolation the product was distilledunder vacuum using a spinning band column. BF. 148 C. 4 torr. Yield 105gm.

(4) Z-plzenyl-S,Q-dimehtyldecmze 100 gms. of the olefin was dissolved in200 ml. of anhydrous ethanol and hydrogenated with the aid of 1.0 gramof 5% palladium on charcoal at a pressure of 40 p.s.i.g. for 4 hours.

Distillation at 5:1 reflux ratio through a spinning band column yielded86 grns. of product. Bl. 140-141 3.9-4.0 torr. n ZO/D 1.4813.

AnaZysfs.Found: (1:87.77, (3:87.73, H=12.27.

EXAMPLE H.2-PHENYL 6,10- DIMETHYLHENDECANE H: 12.24. tl1eor.:

(1 2,6-dimethylhendecanone-Z Pseudoionone, (2,6-dimethylhendeca 2,6,8triene-- one) made by the condensation of citral with acetone washydrogenated at 40 p.s.i.g. and 40 C. over a palladium on charcoalcatalyst until three moles of hydrogen had been absorbed. Distillationunder a spinning-band column gave a pure product showing no unsaturationby infrared spectroscopy. B.P. 118 C. 12 torr. n /1) 1.4345.

(2) Z-plzenyl 6,10-dimetlzylhendecanol-Z A Grignard reagent preparedfrom 173 grams bromobenzene in 500 ml. anhydrous ether and 40 grams ofmagnesium turnings in ml. ether was reacted With 193 grams ofperhydroseudoionone at 5 C. The reaction mixture was then heated underreflux for 3 hours. The reaction products were decomposed with ice andHCl and after removing solvent, distilled under reduced pressure. B.P.C. 1.2 torr. Wt. 245 gms. n 20/D=1.4972.

(3) 2-phenyl 6,1G-dimerhylkendecene-2 The above carbinol was dehydratedby heating with 500 ml. of 60% sufuric acid at 100 C. for 4 hours. Thereaction product was isolated and distilled at reduced pressure. El.97-98" C. 0.025 torr. Wt. 211 guns. n 20/D=1.5029.

(4) Z-phenyl dJO-dimethlyhendecane The above prepared olefin was reducedat 40 p.s.i.g. over a Pd catalyst. The product was fractionated througha spinning-band column. B.P. 8788 C. 0.025 torr. Wt.=189 gins. n20/D=1.4807.

EXAMPLE III.1-PHENY1.-2,6, 1 O-TRIMETHYL- HENDECANE This alkyl benzenewas prepared in the same manner as the product of Example II, exceptthat benzyl chloride was used instead of brorno benzene.

(1) Z-phenyl 2,6,10-zrimethylhendecane-Z The above product was preparedby reacting a Grignard consisting of 18 gm. magnesium, 73 grams benzylchloride and 200 ml. ether with 96 grams perhydroseudoionone. The crudeproduce was stripped to C. (it) 1 torr. without distillation. Wt.=1.34.4grams.

(2) 1 -phenyl 2,6,10-tri'methylhendecene-Z The crude product preparedabove was dehydrated at 100 C. for 4 hours with 500 grams of 60% H 8013.1. 108-110" C. 0.08 torr. Wt. =106.4 guns. n 20/d=1.4950.

(3) I-phenyl 2,6,IO-trimethylherzdecane The above prepared olefindiluted with 250 ml. of absolute ethanol was hydrogenated at 45 C. and40 p.s.i.g. over 2 grams of 5% Pd on charcoal. B.P. 105-160 C. 0.07torr. Wt. :91 gms. n 20/D==1.4872.

EXAMPLE IV.-1-PHENYL 2,5,9- TRIMETHYLDECANE This hydrocarbon is preparedin similar manner to the product of Example I from l-phenyl propanone-2and a Grignard prepared from l-bromo 3,7-dimethyloctane.

EXAMPLE V.1-PHENYL 3,6,10- T RIM ETHYLHENDECANE This hydrocarbon isprepared in similar manner to the product of Example I from l-phenylbutanone-3 and a Grignard prepared from l-bromo 3,7-dimethyloctane.

EXAMPLE VI.-2-PHENYL 7,11-

DIMETHYLDODECANE This hydrocarbon is prepared in similar manner to theproduct of Example I from 3-phenyl butyraldehyde and a Grignard preparedfrom l-bromo 3,7-dimethy1octane.

A number of the alkyl benzenes prepared above were checked for purity bymeans of capillary gas chromatography. Analytical data obtained by thismeans are more precise than a simple carbon and hydrogen analysis.Through the use of two internal standards, namely; benzene andhexadecane, relative retention times were obtained for a number ofproducts. Retention times under the conditions noted below werecalculated on the basis of benzene equal to zero and hexadecane equal to1.00.

7 .CAP'ILLARY GAS CHROMATOGrRAPHY Instrument Barber-Colman.

Column 150 ft. capillary.

Coating Apeizon-L.

Flash heater 213C.

Column heater 200 C.

Cell temp 215 C.

Ionization source Strontium-90.

Carrier gas Argon20 p.s.i.g.

Voltage 1250.-

Product: Retention time l-phenyl dodecane 3.75 2-phenyl dodecane 2.563-phenyldodecane 2.12 4-phenyldodecane 1.87 5-phenyldodecane 1.756-phenyldodecane 1.69 2-phenyl 5,9-dimethyldecane 1.54 2-pheny16,10-dimethylhendecane 2.38 l-phenyl 2,6,IO-trimethylhendecane 3.92l-phenyl 6-cyclohexylhexane 5.55 l-phenyl 5,5,7,7-tetramethyloctane 1.94

EXAMPLE VII Fifty grams of the alkyl benzenes prepared as in the aboveexamples were sulfonated with seventy grams of 20% oleum at a maximumtemperature of 55 C. for a total contact time of one-half hour.Following neutralization with sodium hydroxide, the products Weredeoiled by extraction with petroleum ether and desalted by dehydrationwith excess sodium carbonate from a solution in isopropyl alcohol.Evaporation to dryness under vacuum gave pure dry sulfonates.

EXAMPLE VIII A number of the sulfonates prepared above were tested in astandard dishwashing procedure at a concentration of 0.03% of puredetergent in 8 grain water at a temperature of 120 F. and compared witha standard tetrapropylbenzene sulfonate.

Product: Dishes washed Sod. sulfonate 2-phenyldodecane 16 Sod. sulfonate2-phenyl 5,9-dimethyldecane 31 Sod. sulfonate 2 phenyl 6,10dimethylhendecane 29 Sod. sulfonate tetrapropylbenzene 15 EXAMPLE IXCotton detergency using standard soiled cloth was determined for anumber of sulfonates in a build formulation. All products were tested at0.15 and 0.25% at 120 F. in 8 grain water of the built formulation usingthe following composition.

Wt. percent Test sod. alkyl benzene sulfonate 20 Sodium tripolyphosphate30 Tetrasodium pyrophosphate 10 Sodium metasilicate 5 Sodiumcarboxymethyl cellulose 1 Sodium sulfate 34 Cotton Detergency 0 Increasein Reflectance Concentration (100% Active) 1 0.03% 0.05%

Ootton-SoilType U.S. T.F. U.S. T.F.

2 Phenyldodecanc 9.8 15.2 10.6 15.7 Z-Phenyl5,9-Dimethyldecane 13.9 16.814.5 19.0 2-Phenyl 6,10-Dimethylhendecane 13.9 18.0 16.1 19.3 l-Phenyl2,6,10-Tri1nethylhendecane-.- 15.5 18.8 17.0 19.4 StandardTetrapropylbenzene 4.9 10.3 10.0 12.4

8 EXAMPLE X.-BIODEGRADATION Two types of tests were employed fordetermining the biodegradability of the synthetic detergents preparedaccording to this invention.

In an Activated Sludge Test, fifty milligrams of the detergent alongwith one liter of synthetic sewage was fed daily to aeration unitscontaining approximately 2000 milligrams of activated sludge per liter.Effluent from the unit was removed daily and the residual detergentdetermined by means of methylene-blue and the foaming characteristicsdetermined by blowing a fixed rate of air through a standard volume ofefiluent. Details of this test have been published by I. F. Nelson etal., Developments in Industrial Microbiology Plenum Press, New York,1961.

In a Simulated River Water test the sewage organisms were acclimated tothe detergent for a period of about 2 months and then starved so thatthe only source of food was the synthetic detergent.

The results obtained with these tests are shown below.

ACTIVATED SLUDGE TEST 1 By Methylene-Blue Test. 2 Foam height in cm.

Sodium sulfonates of above alkylbenzenes mgm. per Liter.

SIMULATED RIVER TEST tested at 50 Percent Disappearance 2 Days on Test l26 56 Sod. Sulf. 2-Phenyldodecane 100 100 Sod. 8111!. Example I 93 Sod.Snlf. Example II 96 95 Sod. Suit. Tctrapropylbcnzene--- 0 4 Afterinitial acclimation. 2 By Methylene-Blue.

What is claimed is:

1. The composition of matter RZ-C H --SO H which is the sulfonationproduct of the compound R-ZC H and wherein R is a perhydrobis-(isoprenyl) alkyl radical having predominantly the structureOH;-(fHCH CH OH OHOHT-OH2- CH; H

and Z is a two to four carbon alkylene group, the said alkylene groupcontaining a single methyl side chain.

2. The composition of matter RZ-C H $O M which is the sulfonationproduct of the compound RZC H and wherein R is a perhydrobis-(isoprenyl) alkyl radical having predominantly the structure CH([3HCH -GH -CH -CH-OHg-OH;

CH3 H3 Z is a two to four carbon alkylene group, the said alkylene groupcontaining a single methyl side chain, and M is an alkali metal.

3. The composition of matter 9 10 which is the sulfonation product ofthe compound References Iited by the Examiner CH3 ?H CH2 CHFGHF$H CH2CH2%H C6H5 UNITED STATES PATENTS CH8 3 3 1,934,123 11/33 Hofman et al260-668 wherein M is an alkali metal. 5 2,467,170 4/49 Weinmayr 260-5054. The composition of matter 2,517,720 8/50 Schaad 260-505 OH;CH-CH CH-CH:GHOH CH CH OH-C H;SO M 9 5 5/ 61 F055 26O668 H H 3,009,972 11/61Johnson 260-505 a 3 3,115,530 12/63 Cohen 260-505 which is thesulfonation product of the compound 10 CH -C[HCH GH UH;:CHGH CH CH CH-CH OTHER REFERENCES OH; 0H H3 Bauzngartner: Ind. and Eng. Chem, vol. 46,1954, wherein M is an alkali metal. 1349 1352' The Composition of matter15 Hammenton: J. Appl. Chem, vol. 5, 1955, pp. 517-524. CH -CH-CH CH -CH-CH-CH -CH -CE -CH-CH -C611;S03M References Cited by the Applicant H3 HH3 Gray et al.: Journal of Organic Chemistry, vol. 26, which is thesulfonation product of the compound 209 19 1 CH CH-CH CH CH UHF-CH CHCH2OH=CH C H5 3- H 2 F ii H CH r LORRAINE A. WEINBERGER, PrimaryExaminer.

wherein M is an alkali metal. LEON ZITVER Examiner

1. THE COMPOSITION OF MATTER R-Z-C6H4-SO3H WHICH IS THE SULFONATIONPRODUCT OF THE COMPOUND R-Z-C6H5 AND WHEREIN R IS A PERHYDROBIS-(ISOPRENYL) ALKYL RADICAL HAVING PREDOMINANTLY THE STRUCTURE